trans-Tetra­aqua­bis{(E)-2-cyano-1-[(ethoxy­carbon­yl)methyl­sulfan­yl]-2-(1-naphthyl­amino­carbon­yl)ethene-1-thiol­ato}calcium(II) diethyl ether disolvate

Galal H Elgemeie; Nahed M Fathy; Sayed Shaarawi; Peter G Jones

doi:10.1107/S1600536810013024

. 2010 Apr 21;66(Pt 5):m554–m555. doi: 10.1107/S1600536810013024

trans-Tetraaquabis{(E)-2-cyano-1-[(ethoxycarbonyl)methylsulfanyl]-2-(1-naphthylaminocarbonyl)ethene-1-thiolato}calcium(II) diethyl ether disolvate

Galal H Elgemeie ^a,^*, Nahed M Fathy ^b, Sayed Shaarawi ^b, Peter G Jones ^c

PMCID: PMC2979207 PMID: 21579039

Abstract

In the title compound, [Ca(C₁₈H₁₅N₂O₃S₂)(H₂O)₄]·2C₄H₁₀O, the Ca atom, which lies on an inversion centre, is coordinated octahedrally by four water molecules and two anions of the ketene dithioacetal, the donor atoms of which are the amidic carbonyl O atoms. The central backbone of the ligands (excluding the naphthalene and oxoethyl groups) is essentially planar (r.m.s. deviation 0.035 Å). Intramolecular hydrogen bonds are observed from the NH group to the formally ‘thiolate’ S atom and from one coordinated water to the nitrile group and to the ether O atom. Intermolecular hydrogen bonds from the second independent water molecule to the thiolate S atom and the side-chain oxo group connect the molecules in chains parallel to the a axis.

Related literature

For our studies exploring the synthetic potential of ketene dithioacetals for synthesizing new classes of novel antimetabolic agents, see: Elgemeie & Sood (2006 ▶); Elgemeie et al. (2008 ▶, 2009 ▶). For our reports of successful approaches for the synthesis of mercaptopurine and pyrimidine analogues by the reaction of ketene dithioacetals with active methylene functions, see: Elgemeie (2003 ▶); Elgemeie et al. (2004 ▶, 2007 ▶).

Experimental

Crystal data

[Ca(C₁₈H₁₅N₂O₃S₂)(H₂O)₄]·2C₄H₁₀O
M _r = 1003.26
Triclinic,
a = 7.8665 (3) Å
b = 12.4361 (5) Å
c = 13.8045 (6) Å
α = 103.692 (4)°
β = 99.963 (4)°
γ = 101.609 (3)°
V = 1250.24 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 100 K
0.4 × 0.3 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.970, T _max = 1.000
26853 measured reflections
6443 independent reflections
4941 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.070
S = 0.96
6443 reflections
326 parameters
18 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810013024/bt5223sup1.cif

e-66-0m554-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013024/bt5223Isup2.hkl

e-66-0m554-Isup2.hkl^{(315.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Ca—O1	2.2696 (9)
Ca—O2W	2.3265 (10)
Ca—O1W	2.3434 (10)
S1—C13	1.7686 (12)
S1—C14	1.7891 (12)
S2—C13	1.7037 (12)
O1—C11	1.2494 (14)
N1—C11	1.3448 (15)
N1—C1	1.4184 (15)
N2—C18	1.1518 (16)
C11—C12	1.4684 (16)
C12—C13	1.3996 (17)
C12—C18	1.4325 (17)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H01⋯S2	0.855 (16)	2.279 (16)	3.0274 (11)	146.2 (14)
O1W—H1W⋯O93	0.82 (1)	1.94 (1)	2.7531 (14)	171 (2)
O1W—H2W⋯N2ⁱ	0.82 (1)	2.22 (1)	2.9902 (15)	157 (2)
O2W—H3W⋯O3ⁱⁱ	0.82 (1)	2.03 (1)	2.7797 (13)	151 (2)
O2W—H4W⋯S2ⁱⁱ	0.81 (1)	2.51 (1)	3.2666 (11)	157 (2)

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

Comment

During the course of our studies directed toward exploring the synthetic potential of ketene dithioacetals for synthesizing new classes of novel antimetabolic agents (Elgemeie & Sood, 2006; Elgemeie et al., 2008, 2009), we have recently reported various successful approaches for synthesis of mercaptopurine and pyrimidine analogues by the reaction of ketene dithioacetals with active methylene functions (Elgemeie, 2003; Elgemeie et al., 2004, 2007). In conjunction of this work, we report here a novel calcium salt (I) of a ketene dithioacetal. The structure of (I) was established on the basis of its elemental analysis and spectral data (see Experimental). In order to establish unambiguously the structure of the product, the crystal structure was determined. The X-ray analysis confirms the exclusive presence of the form (I) in the solid state (Figure 1).

The structure consists of a calcium ion on an inversion centre, coordinated octahedrally by four water molecules and two anions of the ketene dithioacetal; the latter coordinate via the amidic carbonyl oxygen O1, with Ca—O1 2.2696 (9) Å. The asymmetric unit also contains one molecule of diethyl ether.

Within the ligand, there is presumably extensive delocalization of the negative charge from its formal position at the "thiolate" sulfur S2 through the ligand backbone (see dimensions in Table 1), in which the ten atoms C1, C11–14, C18, N1, O1, S1 and S2 are approximately coplanar (r.m.s. deviation 0.035 Å). The backbone angles C11—C12—C13 and C12—C13—S2 are noticeably wide at 126.43 (9) and 129.48 (11)° respectively. The Ca atom lies 0.862 (1) Å out of the backbone plane,and the naphthalene plane subtends an interplanar angle to this plane of 29.03 (2)°.

Intramolecular hydrogen bonds (Table 2) are observed from the NH function to the formally thiolate sulfur and from a hydrogen of the coordinated water O1W to the nitrile N. Additionally, the ether molecules are connected by a hydrogen bond from the same water to the ether oxygen. Intramolecular H bonds from the second water to the thiolate sulfur and the 2-oxo function connect the molecules to form chains parallel to the a axis (Fig. 2).

Experimental

The IR spectrum revealed the presence of cyano group at 2190 cm^-1. The ¹H NMR spectrum revealed signals at δ 1.06–1.24 ppm (t, CH₃), 2.51 (s, SCH₂), 4.08–4.15 (qua, ester CH₂) 7.43–8.37 (m, aromatic protons) and 8.40 (br s, NH).